Alexandre Marletta

Investigation of Ground- and Excited-State Photophysical Properties of 5,10,15,20-Tetra(4-pyridyl)-21H,23H-porphyrin with Ruthenium Outlying Complexes

The present work employs a set of complementary techniques to investigate the influence of outlying Ru(II) groups on the ground- and excited-state photophysical properties of free-base tetrapyridyl porphyrin (H(2)TPyP). Single pulse and pulse train Z-scan techniques used in association with laser flash photolysis, absorbance and fluorescence spectroscopy, and fluorescence decay measurements, allowed us to conclude that the presence of outlying Ru(II) groups causes significant changes on both electronic structure and vibrational properties of porphyrin. Such modifications take place mainly due to the activation of nonradiative decay channels responsible for the emission quenching, as well as by favoring some vibrational modes in the light absorption process. It is also observed that, differently from what happens when the Ru(II) is placed at the center of the macrocycle, the peripheral groups cause an increase of the intersystem crossing processes, probably due to the structural distortion of the ring that implies a worse spin-orbit coupling, responsible for the intersystem crossing mechanism.

The Role of Wing Pigmentation, UV and Fluorescence as Signals in a Neotropical Damselfly

Pigmentation patterns, ultraviolet reflection and fluorescent emission are often involved in mate recognition and mate quality functions in many animal taxa. We investigated the role of wing ultra-violet reflection, fluorescence emission, and pigmentation on age and sexual signals in the damselfly Mnesarete pudica. In this species, wings are sexually dimorphic in colour and exhibit age dependency: males and females show a smoky black colouration when young, turning red in mature males while it turns brown in females. First, we investigated wing UV patterns through reflectance and emission spectra. Second, behavioural experiments were undertaken to show male and female responses to manipulated wing pigmentation and experimentally reduced UV (UV-). Reflectance spectra of the wings of juvenile and mature males and females were used to show the differences between controls and individuals with manipulated colouration used in the behavioural experiment. UV-reduced, females with wings painted red, and control males and females were tethered and presented to conspecific males and females, and their behavioral responses were recorded. The male red wing pigmentation and females with red wings elicited an aggressive response in territorial males and a sexual response in females. Both males and females showed neutral responses towards individuals with reduced UV. Wing signals of juvenile individuals also provoked neutral responses. These results suggest that UV, together with pigmentation, plays a role during mate recognition in males and females. Other than butterflies and spiders, it seems that fluorescence signals and UV reflectance can also be part of communication in odonates.

Photoinduced photoluminescence intensity enhancement in poly(p-phenylene vinylene) films

We report measurements of photoluminescence (PL) intensity enhancement in poly(p-phenylene vinylene) (PPV) films induced by light irradiation in the presence of air. This effect is dependent on laser intensity and the ratio between film thickness and excitation penetration depth. The results suggest that an efficient spectral diffusion of excited carriers to nondegraded PPV segments by Forster energy transfer is an important consideration in the PL efficiency of conjugated polymers light-irradiated in air.

Self-assembly of poly(p-phenylene vinylene) using long chain counter-ion: a new process for fabrication of multilayer thin films heterostructures

Layer-by-layer thin films of sulfoniun poly(p-phenylene vinylene) (PPV) precursor have been processed using the long chain dodecylbenzenesulfonate (DBS) anion. Here we adopted the alternative approach consisting of the controlled substitution of the chloride counterion of a water-soluble PPV precursor by DBS. The internal layer structure of these films is therefore likely to be different from conventional layer-by-layer films, since DBS ions are expected to be incorporated into the PPV precursor chain. The main advantage of this novel procedure is that thermal conversion through the elimination of DBS may be realized at considerably lower temperatures (80-100 °C) in a few minutes, with enhanced optical properties. Using this new conversion procedure, the conjugation length can also be varied along the deposition direction by controlling the immersion time or DBS concentration in the film. This opens up a number of new possibilities to realize molecularly band-gap engineered structures such as asymmetric ladder type or V-type structures along the film.

Substrate/semiconductor interface effects on the emission efficiency of luminescent polymers

The importance of interface effects for organic devices has long been recognized, but getting detailed knowledge of the extent of such effects remains a major challenge because of the difficulty in distinguishing from bulk effects. This paper addresses the interface effects on the emission efficiency of poly(p-phenylene vinylene) (PPV), by producing layer-by-layer (LBL) films of PPV alternated with dodecylbenzenesulfonate. Films with thickness varying from ∼15 to 225 nm had the structural defects controlled empirically by converting the films at two temperatures, 110 and 230 °C, while the optical properties were characterized by using optical absorption, photoluminescence (PL), and photoluminescence excitation spectra. Blueshifts in the absorption and PL spectra for LBL films with less than 25 bilayers (<40–50 nm) pointed to a larger number of PPV segments with low conjugation degree, regardless of the conversion temperature. For these thin films, the mean free-path for diffusion of photoexcited carriers ...

Modeling adsorption processes of poly-p-phenylenevinylene precursor and sodium acid dodecylbenzenesulfonate onto layer-by-layer films using a Langmuir-type metastable equilibrium model.

The adsorption kinetics curves of poly(xylylidene tetrahydrothiophenium chloride) (PTHT), a poly-p-phenylenevinylene (PPV) precursor, and the sodium salt of dodecylbenzene sulfonic acid (DBS), onto (PTHT/DBS)n layer-by-layer (LBL) films were characterized by means of UV-vis spectroscopy. The amount of PTHT/DBS and PTHT adsorbed on each layer was shown to be practically independent of adsorption time. A Langmuir-type metastable equilibrium model was used to adjust the adsorption isotherms data and to estimate adsorption/desorption coefficients ratios, k=kads/kdes, values of 2x10(5) and 4x10(6) for PTHT and PTHT/DBS layers, respectively. The desorption coefficient has been estimated, using literature values for poly(o-methoxyaniline) desorption coefficient, as was found to be in the range of 10(-9) to 10(-6) s(-1), indicating that quasi equilibrium is rapidly attained.

Vibrational structure of organic semiconductors: the role of conjugation length

Site-selective luminescence spectroscopy (SSL) was employed to resolve the vibracional modes in self-assembled poly(p-phenylene vinylene), PPV. Using Franck-Condon analysis, the PPV spectra can be well described by three effective vibrational modes at 330, 1160 and 1550 cm-1. As the temperature increases from 4 to 180 K the electron-phonon coupling (S factor) remains constant for the 1550 cm-1 mode while for other lower energy modes the coupling increases monotonically. This trend is consistent with the decrease of the conjugation length due to the increase of thermal disorder. We find that the temperature dependence of vibrational progression in PPV films is determined mainly by low frequency torsional modes.

Circular dichroism and circularly polarized luminescence of highly oriented Langmuir-Blodgett films of poly(p-phenylene vinylene)

Langmuir-Blodgett films of a poly(p-phenylene vinylene) (PPV) precursor were prepared using an amphiphilic precursor, where the counter-ion chloride was partially exchanged by a long chain dodecylbenzenesulfonate (DBS) ion. These LB-PPV films are strongly ordered along the dipping direction as demonstrated by linear dichroism experiments using linearly polarized optical absorption and emission. The consequence of this anisotropy is a strong circular dichroism (100 mdeg) in the π-π band and a circular polarization emission with an asymmetry factor g e =0.84.

Glass transition of polystyrene (PS) studied by Raman spectroscopic investigation of its phenyl functional groups

In polymeric materials the glass transition (GT) is a well-known and very important relaxation process related to movements of functional groups in the polymeric chain. In this work, we show the potential of Raman spectroscopy for exploring the GT process in the polymer polystyrene. We collected Raman spectra during a step-by-step heating process of the sample, which allowed us to collect signatures of the GT process from peak parameters of specific vibrational modes, and to verify the GT temperature. Results of the latter were in accordance with published values obtained via other methods. We identified the aromatic ring vibrational modes of the phenyl functional groups to be those which, due to steric hindrance, suffer the largest influence during the GT process. This confirms that Raman spectroscopy can be used as a complementary technique to perform GT investigations in polymeric materials due to its sensitivity to small intermolecular changes affecting vibrational properties of relevant functional side groups.

A new designed π conjugated molecule for stable single walled carbon nanotube dispersion in aqueous medium

A molecule with a π conjugated backbone built from aromatic thiophene and dialkoxyphenylene units and substituted imidazolium groups (TPO) is designed to obtain ultra-stable single walled carbon nanotube (SWCNT) dispersion in aqueous medium. The proposed mechanism of non-covalent interaction is accompanied by individualization of SWCNT and comprises of dominant nondisruptive π-π and cation-π interaction between them and the TPO conjugated oligomer. The individualization of SWCNT and dispersibility and stability of the ultra-stable suspensions were estimated using high resolution transmission electron microscopy, UV-Visible-NIR absorption spectroscopy, Raman spectroscopy, photoluminescence and zeta potential measurement. Nuclear magnetic resonance data provides direct evidence toward possible cation-π interaction.